Three-component catalyst containing polymeric methyl halide-metal reaction product and titanium compound for olefin polymerization



United States Patent 3,026,310 THREE-CGMPGNENT CATALYST CONTAINING POLYMIEFJC METHYL HALDE-METAL REAC- TIGN PRQDUCT AND TITANIUM COMPOUND FOR CLEFIN PQLYBTEREZATION Newton H. Shemer, 3L, and Harry W. Coover, Jr., Kingsport, Tenn, assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New .lersey No Drawing. Filed Mar. 31, 1958, Ser. No. 724,918 15 Claims. (Cl. 260-931) This invention relates to a new and improved polymerization process and is particularly concerned with the use of a novel catalyst combination for preparing high molecular weight solid polyolefins, such as polypropylene, of high density and crystallinity. In a particular aspect the invention is concerned with the preparation of polypropylene and higher polyolefins using a particula catalyst which has unexpected catalytic activity and which gives products characterized by unusually high crystallinity, softening point, thermal stability, stiifness and being substantially free of non-crystalline polymers.

Polyethylene has heretofore been prepared by high pressure processes to give relatively flexible polymers having a rather high degree of chain branching and a density considerably lower than the theoretical density. Thus, pressures of the order of 500 atmospheres or more and usually of the order of 1000-4500 atmospheres are commonly employed. It has been found that more dense polyethylenes can be produced by certain catalyst cornbinations to give polymers which have very little chain branching and a high degree of crystallinity. The exact reason why certain catalyst combinations give these highly dense and highly crystalline polymers is not readily understood. Furthermore, the activity of the catalysts ordinarily depends upon certain specific catalyst combinations, and the results are ordinarily highly unpredictable, since relatively minor changes in the catalyst combination often lead to liquid polymers rather than the desired solid polymers.

This application is a continuation-in-part of our copending application, Serial No. 549,868, filed November 29, 1955. In that application we have described the polymerization of a-olefinic hydrocarbons in the presence of a catalyst containing a titanium compound and the polymeric reaction product of a methylene halide with a metal from the group consisting of aluminum, zinc and magnesium. Such catalysts are quite effective for polymerizing ethylene to form a solid crystalline product. However, when such catalysts are used to polymerize propylene and higher m-oleiinic hydrocarbons, the product is predominantly polymeric oils and rubbers with a comparatively small amount of high molecular weight, crystalline product. These facts indicate that one cannot predict whether a specific catalyst combination will be effective to produce crystalline, high density polymers with specific a-olefins and that, when a crystalline product is desired, the above catalysts are inadequate for polymerizing propylene and higher a-olefins.

This invention is concerned with and has for an object the provision of improved processes whereby a-monoolefins and particularly propylene and higher a-olefins can be readily polymerized by catalytic means to give high molecular weight, highly crystalline polymers. A particular object of the invention is to provide a catalyst combination which has unexpected catalytic activity for the polymerization of u-monoolefins to form crystalline high density polymers. Other objects will be apparent from the description and claims which follow.

These and other objects which will be apparent from the description and claims which follow are attained by means of the process embodying the present invention ICC wherein a-monoolefins, either singly or in admixture, are readily polymerized to high molecular weight solid crystalline polymers by effecting the polymerization in the presence of a catalytic mixture of a titanium compound, a nondistillable polymeric reaction product resulting from reaction of a methylene halide with a metal from the group consisting of aluminum, zinc and magnesium, and.

a group VA compound. The titanium compound em ployed is desirably a titanium tetrahalide or. a titanium tetraalkoxide but can be other well known titanium compounds such as a titanium oxide or mixture of oxides. The polymeric reaction product forming the second component of the catalyst mixture is the product obtained by reacting a methylene halide, such as methylene bromide or chloride, with aluminum, magnesium, or zinc, and is a complex material of polymeric nature whose structure is not readily definable. The polymeric reaction product of a methylene halide and aluminum is preferred, although the other materials defined can be used with somewhat less advantageous results.

Particularly good results are obtained using a titanium tetrachloride, tetrabromide or tetraalkoxide wherein each alkoxide group contains 1-4 carbon atoms, and a polymeric reaction product of methylene chloride with aluminum. The polymeric reaction products obtained in this manner by substituting magnesium for aluminum also gave excellent results approaching those obtained with the aluminum compounds whereas the zinc complexes are less preferably used but gave high effective results in many cases. The third component of the catalyst is a group VA compound having the formula R Z wherein Z is selected from the group consisting of nitrogen, phosphorus, arsenic and antimony and each R is selected from the group consisting of hydrogen and hydrocarbon radicals containing 1-12 carbon atoms and selected from the group consisting of alkyl, aryl and aralkyl. Among these hydrocarbon radicals are methyl, ethyl, propyl, butyl, octyl, dodecyl, phenyl, phenylethyl and naphthyl. In the group VA compound the three radicals represented by R can be the same or different. The catalytic activity of this mixture was wholly unexpected, particularly since the mixture, in the absence of the group VA compound produces large amounts of oils and rubbers when propylene and higher a-II10l10016fiI1S are polymerized. Also the third component of this catalyst composition is not an effective polymerization catalyst. The inventive process is carried out in liquid phase in an inert organic liquid and preferably an inert liquid hydrocarbon vehicle, but the process can be carried out in the absence of an inert diluent. The process proceeds with excellent results over a temperature range of from 0 C to 250 C., although it is preferred to operate within the range of from about 50 C. to about C. Likewise, the reaction pressures may be varied widely from about atmospheric pressure to very high pressures of the order of 20,000 psi. or higher. A particular advantage of the invention is that pressures of the order of 30-1000 p.s.i. give excellent results, and it is not necessary to employ the extremely high pressures which were necessary heretofore. The liquid vehicle employed is desirably one which serves as an inert liquid reaction medium.

The invention is of particular importance in the preparation of highly crystalline polypropylene, the polybutenes and polystyrene although it can be used for polymerizing mixtures of ethylene and propylene as well as other a-HlQIlOOlCfiIlS containing up to 10 carbon atoms. The polypropylene produced has a softening point above C. and a density of 0.91 and higher. Usually the de9n2sity of. the polypropyene is of the order of 0.91 to 0.

The polyolefins prepared in accordance with the invention can be molded or extruded and can be used to form plates, sheets, films, or a variety of molded objects which exhibit a higher degree of stiffness than do the corresponding high pressure polyolefins. The products can be extruded in the formof pipe or tubing of excellent rigidity and can be injection molded into a great Variety of articles. -The polymers can also be cold drawn into ribbons, bands, fibers or filaments of high elasticity and rigidity; Fibers of high strength can be spun from the molten polyolefins obtained according to this process.

Theimproved results obtained in accordance with the invention depend upon the particular combination of catalyst materials defined herein. The polymeric reaction products for the catalyst are readily prepared by reacting methylene bromide, methylene chloride, or the like with the desired aluminum, magnesium or zinc in the form of granules, turnings, or powder. The reaction proceeds readily with the evolution of heat to form nondistillable polymeric solids. In some cases, it is desirable to initiate the reaction by the addition of a crystal of iodine or preferably by the addition of a small amount of previously prepared polymeric reaction product. In some cases, it also assists the reaction to heat it initially on a steam bath. During the course of the reaction, it is usually desirable to control the heat of reaction by cooling the reaction mixture. When the evolution of heat has ceased, the reaction mixture can he refluxed to ensure completion. The nondistillable polymeric reaction product solidifies on cooling and can be used directly as catalyst for the polymerizations embodying the invention. The polymeric reaction product must be protected from atmospheric oxygen and moisture before and during use. The exact nature of the polymeric reaction products is not readily understood, and the invention will not be limited by any attempt to define the exact composition. The catalyst combination also contains one or more titanium compounds. Titanium tetrachloride and tetrabromide are preferably employed, although excellent results are obtained with the titanium tetraalkoxides containing 1-4 carbon atoms in each alkoxide group, such as titanium tetrabu-toxide, titanium tetramethoxide, titanium tetraethoxide and the like. Good results are also obtained using such other titanium compounds as titanium dioxide, titanium sesquioxide, and mixtures thereof. The third component of the catalyst composition is a compound of a group VA element having the structural'formula R 2 wherein Z is a group VA element selected from the group consisting of nitrogen, phosphorus, arsenic and antimony. Each R is a radical selected from the group consisting of hydrogen and hydrocarbon radicals containing 1-12 carbon atoms as defined hereinabove. Preferably R is selected from the group consisting of lower alkyl containing from 14 carbon atoms and phenyl. In this third component the R radicals can be the same but in some instances it is desired to employ different radicals within the definition set forth above. Among the specific compoundsthat can be used are tributylamine, diethylaniline, tributyl phosphine, triphenylphosphine, triphenylarsine, triphenylstibine and the like. The catalyst compositions of this invention, when reacted with water, do not produce hydrogen.

The limiting factor inthe temperature of the process appears to be the decomposition temperature of the catalyst. Ordinarily temperatures from '50" C. to 150 C. areemployed, although'temperatures as low as 0 C. or as high as 250 C. can be employed if desired. Usually, it is not desirable or economical to effect the polymerization at temperatures below 0 C., and the process can be readily controlled at room temperature or higher which is an advantage from thestandpoint of commercial processing. The pressure employed is usually only sufficient to maintain the reaction mixture in liquid form during the polymerization, although higher pressures can be used if desired. The pressure is ordinarily achieved by pressuring the system with the monomer whereby ad ditional monomer dissolves in the reaction vehicle as the polymerization progresses.

The polymerization embodying the invention can be carried out batchwise or in a continuous flowing stream process. The continuous processes are preferred for economic reasons, and particularly good results are obtained using continuous processes wherein a polymerization mixture of constant composition is continuously and progressively introduced into the polymerization zone and the mixture resulting from the polymerization is continuously and progressively Withdrawn from the polymerization zone at an equivalent rate, whereby the relative concentration of the various components in the polymerization zone remains substantially unchanged during the process. This results in formation of polymers of extremely uniform molecular weight distribution over a relatively narrow range. Such uniform polymers possess distinct advantages since they do not contain any substantial amount of the low molecular Weight or high molecular weight formations which are ordinarily found in polymers prepared by batch reactions.

In the continuous flowing stream process, the temperature is desirably montained at a substantially constant value within the preferred range in order to achieve the highest degree of uniformity. Since it is desirable to employ a solution of the monomer of relatively high concentration, the process is desirably effected under a pressure of from 30 to 1000 psi. obtained by pressuring the system with the monomer being polymerized. The amount of vehicle employed can be varied over rather wide limits with relation to the monomer and catalyst mixture. Best results are obtained using a concentration of catalyst of from about 0.1% to about 2% by weight based on the Weight of the vehicle. The concentration of the monomer in the vehicle will vary rather Widely depending upon the reaction conditions and will usually range from about 2 to 50% by weight. For a solution type of process it is preferred to use a concentration from about 2 to about 10% by Weight based on the weight of the vehicle, and for a allury type of process higher concentrations, for example, up to 40% and higher are preferred. Higher concentrations of monomer ordinarily increase the rate of polymerization, but concentrations above 510% by weight in a solution process are ordinarily less desirable because the polymer dissolved in the reaction medium results in a very viscous solution.

In preparing the polymeric reaction products for the catalyst, the ratio of methylene halide to aluminum, zinc or magnesium can be varied widely, although the metal is ordinarily employed in molar excess to ensure completion of the reaction. Any unused metal can be readily separated from the molten polymeric reaction product. The molar ratio of polymeric organo metallic reaction product to titanium compound can be varied rather widely within the range of from 1:4 to 16:1. Excellent results are obtained with approximately equal weights of the two components of the catalyst mixture or with a slight excess by weight of the titanium compound. The group VA compound is preferably used in an amount within the range of 0.1 to 1 mole. The polymerization time can be varied as desired and will usually be of the order of from 30 minutes to several hours in batch processes. Contact times of from 1 to 4 hours are commonly employed in autoclave type reactions. When a continuous process is employed, the contact time in the polymerization zone can also be regulated as desired, and in some cases it is not necessary to employ reaction or contact times much beyond one-half to one hour since a cyclic system can be employed by precipitation of the polymer and return of the vehicle and unused catalyst to the charging zone wherein the catalyst can be replenished and additional monomer introduced.

The organic vehicle employed can be an aliphatic alkane or cycloalkane such as pentane, hexane, heptane or cyclohexane, or a hydrogenated aromatic compound such as tetrahydronaphthalene or decahydronaphthalene, or a high molecular weight liquid parafiin or mixture of parafiins which are liquid at the reaction temperature, or an aromatic hydrocarbon such as benzene, toluene, Xylene, or the like, or a halogenated aromatic compound such as chlorobenzene, chloronaphthalene, or orthodichlorobenzene. The nature of the vehicle is subject to considerable variation, although the vehicle employed should be liquid under the conditions of reaction and relatively inert. The hydrocarbon liquids are desirably employed. Other solvents which can be used include ethyl benzene, isopropyl benzene, ethyl toluene, n-propyl benzene, diethyl benzenes, mono and dialkyl naphthalenes, n-octane, iso-octane, methyl cyclohexane, tetralin, decalin, and any of the other well-known inert liquid hydrocarbons. The diluents employed in practicing this invention can be advantageously purified prior to use in the polymerization reaction by contacting the diluent, for example, in a distillation procedure or otherwise, with the polymerization catalyst to remove undesirable trace impurities. Also, prior to such purification of the diluent the catalyst can be contacted advantageously with polymerizable a-monoolefin.

The polymerization ordinarily is accomplished by merely admixing the components of the polymerization mixture, and no additional heat is necessary unless it is desired to eifect the polymerization at an elevated temperature in order to increase the solubility of polymeric product in the vehicle. When the highly uniform polymers are desired employing the continuous process wherein the relative proportions of the various components are maintained substantially constant, the temperature is desirably controlled within a relatively narrow range. This is readily accomplished since the solvent vehicles forms a. high percentage of the polymerization mixture and hence can be heated or cooled to maintain the temperature as desired.

Thus, by means of this invention polyolefins such as polypropylene, the polybutenes, polystyrene, and the like are readily produced using a catalyst combination which, based on the knowledge of the art, would not be expected to produce the results obtained. The polymers thus obtained can be extruded, mechanically milled, cast or molded as desired. The polymers can be used as blending agents with the relatively more flexible high pressure polyethylenes to give any desired combination of properties. The polymers can also be blended with antioxidants, stabilizers, plasticizers, fillers, pigments, and the like, or mixed with other polymeric materials, waxes and the like. In general, aside from the relatively higher values for such properties as softening point, density, stiifness and the like, the polymers embodying this invention can be treated in similar manner to those obtained by other processes.

From the detailed disclosure of this invention it is quite apparent that in this polymerization procedure a novel catalyst, not suggested in prior art polymerization procedures, is employed. As a result of the use of this novel catalyst it is possible to produce polymeric hydrocarbons, particularly polypropylene, having properties not heretofore obtainable. For example, polypropylene prepared in the presence of catalyst combinations within the scope of this invention is substantially free of rubbery and oily polymers and thus it is not necessary to subject such polypropylene of this invention to extraction procedures in order to obtain a commercial product. Also polypropylene produced in accordance with this invention possesses unexpectedly high crystallinity, an unusually high softening point and outstanding thermal stability. Such polypropylene also has a very high stiffness as a result of the unexpectedly high crystallinity. The properties imparted to polypropylene prepared in accordance with this invention thus characterize and distinguish this polypropylene from polymers prepared by prior art polymerization procedures.

The novel catalysts defined above can be used to produce high molecular weight crysztalline polymeric hydrocarbons. The molecular weight of the polymers can be varied over a wide range by introducing hydrogen to the polymerization reaction. Such hydrogen can be introduced separately or in admixture with the olefin monomer. The polymers produced in accordance with this invention can be separated from polymerization catalyst by suitable extraction procedures, for example, by washing with water or lower aliphatic alcohols such as methanol.

The catalyst compositions have been described above as being effective primarily for the polymerization of ozmonoolefins. These catalyst compositions can, however, be used for polymerizing other oc-olefins, and it is not necessary to limit the process of the invention to monoolefins. Other a-olefins that can be used are butadiene, isoprene, 1,3-pentadiene and the like.

The following examples are illustrative of this invention.

Example 1 In a nitrogen-filled dry box 2 grams of catalyst was added to a 500 ml. pressure bottle containing ml. of dry heptane. The catalyst was made up of the polymeric methylene chloride-aluminum reaction product and titanium tetrachloride in a molar ratio of 1:1. The pressure bottle was then attached to a propylene source and the reaction mixture was agitated at 55 C. under 30 p.s.i. of propylene pressure for 6 hours. No solid polypropylene was produced, although 31.5 g. of oil was isolated. This oil was shown by gas chromatography to consist largely of dimer, trimer, and tetramer of propylene. This demonstrates the inefiectiveness of this catalyst as a means for polymerizing propylene to a solid crystalline polymer.

Example 2 The procedure described in Example 1 was followed using 2 grams of a catalyst made up of polymeric methylene chloridealuminum reaction product, titanium tetrachloride and tributylamine in a molar ratio of 1:1:0.5. During the 6-hour period of agitation of the reaction mixture at 55 C. under 30 p.s.i. propylene pressure, there was formed 10.5 grams of highly crystalline propylene having a density of 0.918 and an inherent viscosity of 3.38 in tetralin at C. The polymer was readily molded into a hard, clear button having a softening point of 165 C.

When polymeric methylene chloride-aluminum reaction product in the above catalyst formulation was replaced by polymeric methylene chloride-zinc reaction product, an equally efiicient catalyst was formed, and under similar conditions the use of this catalyst resulted in the production of 12.1 grams of highly crystalline polypropylene.

Example 3 In a nitrogen-filled dry box a SOD-ml. pressure bottle was loaded with 100 ml. of dry heptane and 2 grams of a catalyst made up of polymeric methylene chloride-aluminum reaction product and titanium tetrabutoxide in a 16:1 molar ratio. The pressure bottle was then attached to a propylene source and the reaction mixture was agitated at 70 C. and under 30 p.s.i. of propylene pressure for 6 hours. No solid propylene polymer was obtained. However, 54 grams of liquid, low-molecular weight polymers were formed. Analysis by gas chromatography indicated that this product contained propylene dimers, trimers, and tetramers.

Example 4 The process of Example 3 was followed using a Z-gram catalyst charge containing polymeric methylene chloridealuminum reaction product, titanium tetrabutoxide, and triphenylphosphine in a 16:1:1 molar ratio. An 8.8 gram yield of solid polypropylene was produced. This solid polymer was extracted with butyl ether to remove a small quantity of rubbery polypropylene and then extracted with heptane to remove the low molecular Weight, crystalline polypropylene. The residual 7.0 grams of polypropylene was highly crystallinezdensity 0.919, inherent viscosity 2.47, and softening point 160-164 C.

Example Inside a nitrogen-filled dry box a 280 ml. stainless steel autoclave was loaded with 0.75 gram of a catalyst having a 1:4:0.l molar ratio of polymeric methylene chloridealurninum reaction product, titanium tetrabutoxide, and diethylaniline. The autoclave was sealed, placed in a rocker, and 100 ml. (51 grams) of propylene was added. Rocking was initiated and the mixture was heated to 85 C. for 4 hours. A yield of 31.0 grams of highly crystalline polypropylene was obtained having a density of 0.918 and an inherent viscosity of 2.91. Tributylphosphine, triphenylarsine, and triphenylstibine, when used in place of diethylaniline, produce desirable yields of highly crystalline polypropylene.

Example 6 The process of Example 5 was followed using 0.5 gram of a catalyst consisting of polymeric methylene chloridealuminum reaction product, titanium tetrachloride, and triphenylphosphine in a 1:l:0.25 molar ratio. A 16.4 gram yield of crystalline polypropylene was obtained having a density of 0.916 and an inherent viscosity of 2.87. Similar results were obtained when diethylaniline was used in place of triphenylphosphine.

Example 7 The process of Example 5 was followed using 3-methyll-butene as the monomer and using a total of 0.1 gram of catalyst at a polymerization temperature of 150 C. A 9.5 gram yield of highly crystalline poly-3-methyl-1-butone was obtained. Good yields of highly crystalline polymer were also obtained using 4-methyl-1-pentene, l-butene, l-pentene, vinylcyclohexane, styrene, and fiuorostyrene as monomers.

We claim:

1. In a polymerization of a-olefinic hydrocarbon material to form solid crystalline polymer, the improvement which comprises catalyzing the polymerization with a catalytic mixture of 1) a nondistillable polymeric solid resulting from reaction of a methylene halide with a metal from the group consisting of aluminum, zinc and magnesium, (2) a titanium compound selected from the group consisting of titanium halides, titanium alkoxides and titanium oxides and (3) a compound of a group VA element having the formula R Z wherein Z is a group VA element selected from the group consisting of nitrogen, phosphorus, arsenic and antimony and each R is a radical selected from the group consisting of hydrogen and hydrocarbon radicals containing 1 to 12 carbon atoms selected from the group consisting of alkyl, aryl and aralkyl, the molar ratio of component 1 to component 2 to component 3 in said catalytic mixture being Within the range of 1:4:0.1 to 16: 1:1.

2. In the polymerization of propylene to form solid crystalline polymer, the improvement which comprises effecting the polymerization in liquid dispersion in an inert organic liquid and in the presence of (1) a nondistillable polymeric solid resulting from reaction of a methylene halide with a metal from the group consisting of aluminum, zinc and magnesium, (2) a titanium compound selected from the group consisting of titanium halides, titanium alkoxides and titanium oxides, and (3) a compound of a group VA element having the formula R Z wherein Z is a group VA element selected from the group consisting of nitrogen, phosphorus, arsenic and antimony and each R is a radical selected from the group consisting of hydrogen and hydrocarbon radicals containing 1 to 12 carbon atoms selected from the group consisting of alkyl, aryl and aralkyl, the molar ratio of component 1 to component 2 to component 3 in said catalytic mixture being within the range of 12410.1 to 16:1:1.

3. In the polymerization of propylene to form solid crystalline polymer, the improvement which comprises effecting the polymerization in liquid dispersion in an inert organic liquid and in the presence of a catalytic mixture of (l) nondistillable polymeric solid methylene halidealuminum reaction product, (2) a titanium tetrahalide, and (3) a compound of a group VA element having the formula R Z wherein Z is a group VA element selected from the group consisting of nitrogen, phosphorus, arsenic and antimony and each R is a radical selected from the group consisting of hydrogen, and hydrocarbon radicals containing 1 to 12 carbon atoms selected from the group consisting of alkyl, aryl and aralkyl, the molar ratio of component 1 to component 2 to componentS in said catalytic mixture being within the range of l:4:0.1 to 16: 1: 1.

4. In the polymerization of propylene to form solid crystalline polymer, the improvement which comprises effecting the polymerization in liquid dispersion in an inert organic liquid and in the presence of a catalytic mixture of (l) nondistillable polymeric solid methylene chloridealuminum reaction product, (2) titanium tetrachloride, and (3) triphenyl phosphine, the molar ratio of component l to component 2 to component 3 in said catalytic mixture being within the range of 1:4:0.1 to 16:1:1.

5. In the polymerization of propylene to form solid crystalline polymer, the improvement which comprises effooting the polymerization in liquid dispersion in an inert organic liquid and in the presence of a catalytic mixture of (1) nondistillable polymeric solid methylene chloridealuminum reaction product, (2) titanium tetrachloride, and (3) tributyl amine, the molar ratio of component 1 to component 2 to component 3 in said catalytic mixture being Within the range of l:4:0.1 to 16:1:1.

6. In the polymerization of propylene to form solid crystalline polymer, the improvement which comprises effooting the polymerization in liquid dispersion in an inert liquid hydrocarbon vehicle and in the presence of a catalytic mixture of (l) nondistillable polymeric solid methylene-chloride-aluminum reaction product, (2) a titanium tetraalkoxide wherein the alkoxide radicals contain 1 to 4 carbon atoms, and (3) triphenyl phosphine, the molar ratio of component 1 to component 2 to component 3 in said catalytic mixture being within the range of 1:4:0.1 to 16:1:1.

7. In the polymerization of propylene to formsolid crystalline polymer, the improvement which comprises effecting the polymerization in liquid dispersion in an inert liquid hydrocarbon vehicle and in the presence of a catalytic mixture of (1) nondistiilable polymeric solid methylene chloride-aluminum reaction product, (2) titanium tetrachloride and (3) diethylaniline, the molar ratio of component 1 to component 2 to component 3 in said catalytic mixture being within the range of 1:4:0.1 to 16: I :1.

8. In the polymerization of propylene to form solid crystalline polymer, the improvement which comprises effecting the polymerization in liquid dispersion in an inert liquid hydrocarbon vehicle and in the presence of a catalytic mixture of (1) nondistillable polymeric solid methylene chloride-zinc reaction product, (2) titanium tetrachloride, and (3) L-ibutylamine, the molar ratio of component 1 to component 2 to componentj in said catalytic mixture being within the range of 1:4:0.l to 16:1:1.

9. As a composition of matter, a polymerization catalyst containing 1) a nondistillable polymeric solid reaction product of a methylene halide with a metal from the group consisting of aluminum, zinc and magnesium (2) a titanium compound selected from the group consisting of titanium halides, titanium alkoxides and titanium oxides, and 3) a compound of a group VA element selected from the group consisting of nitrogen, phosphorus, arsenic and antimony and each R is a radical selected from the group consisting of hydrogen and hydrocarbon radicals containing 1 to 12 carbon atoms selected from the group consisting of alkyl, aryl and aralkyl, the molar ratio of component 1 to component 2 to component 3 in said catalytic mixture being within the range of 12420.1 to 16:1:1.

10. As a composition of matter, a polymerization catalyst containing (1) a nondistillable polymeric solid methylene-halide-aluminum reaction product, (2) a titanium tetrahalide, and (3) a compound of a group VA element having the formula R Z wherein Z is a group VA element selected from the group consisting of nitrogen, phosphorus, arsenic and antimony and each R is a radical selected from the group consisting of hydrogen and bydrocarbon radicals containing 1 to 12 carbon atoms selected from the group consisting of alkyl, aryl and aralkyl, the molar ratio of component 1 to component 2 to component 3 in said catalytic mixture being within the range of 1:4:0.1 to 16:1:1.

11. As a composition of matter, a polymerization catalyst mixture of (1) nondistillable polymeric solid methylene chloride-aluminum reaction product, (2) titanium tetrachloride, and (3) triphenyl phosphine, the molar ratio of component 1 to component 2 to component 3 in said catalytic mixture being within the range of 1:4:0.1 to 16:121.

12. As a composition of matter, a polymerization catalyst mixture of (1) nondistillable polymeric solid methylene chloride-aluminum reaction product, (2) titanium tetrachloride, and (3) tributyl amine, the molar ratio of component 1 to component 2 to component 3 in said catalytic mixture being within the range of 1:4:0.1 to 16:1:1.

13. As a composition of matter, a polymerization catalyst mixture of (1) nondistillable polymeric solid methylene chloride-aluminum reaction product, (2) a titanium tetraalkoxide wherein the alkoxide radicals contain 1 to 4 carbon atoms, and (3) triphenyl phosphine, the molar ratio of component 1 to component 2 to component 3 in said catalytic mixture being Within the range of 1:4:0.1 to 16:1:1.

14. As a composition of matter, a polymerization catalyst mixture of (1) nondistillable polymeric solid methylene chloride-aluminum reaction product, (2) titanium tetrachloride and (3) diethylaniline, the molar ratio of component 1 to component 2 to component 3 in said catalytic mixture being Within the range of 1:4:0.1 to 16:1: 1.

15. As a composition of matter, a polymerization catalyst mixture of (1) nondistillable polymeric solid methylene chloride-zinc reaction product, (2) titanium tetrachloride, and (3) tributylamine, the molar ratio of component 1 to component 2 to component 3 in said catalytic mixture being within the range of 1:4:0.1 to 16:1:1.

References Cited in the file of this patent UNITED STATES PATENTS 2,529,315 Serniuk Nov. 7, 1950 2,832,759 Nowlin et al. Apr. 29, 1958 2,846,427 Findlay Aug, 5, 1958 2,899,416 Schreyer Aug. 11, 1959 2,905,645 Anderson et al. Sept. 22, 1959 FOREIGN PATENTS 781,837 Great Britain Aug. 28, 1957 OTHER REFERENCES The Chemistry of Organometallic Compounds (Rochow), published by John Wiley & Sons, Inc. (London 1957, page relied on). 

1. IN A POLYMERIZATION OF A-OLEFINIC HYDROCARBON MATERIAL TO FORM SOLID CRYSTALLINE POLYMER, THE IMPROVEMENT WHICH COMPRISES CATALYZING THE POLYMERIZATION WITH A CATALYTIC MIXTURE OF (1) A NONDISTILLABLE POLYMERIC SOLID RESULTING FROM REACTION OF A METHYLENE HALIDE WITH A METAL FROM THE GROUP CONSISTING OF ALUMINUM, ZINC AND MAGNESIUM, (2) A TITANIUM COMPOUND SELECTED FROM THE GROUP CONSISTING OF TITANIUM HALIDES, TITANIUM ALKOXIDES AND TITANIUM OXIDES AND (3) A COMPOUND OF A GROUP VA ELEMENT HAVING THE FORMULA R3Z WHEREIN Z IS A GROUP VA ELEMENT SELECTED FROM THE GROUP CONSISTING OF NITROGEN, PHOSPHORUS, ARSENIC AND ANTIMONY AND EACH R IS A RADICAL SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND HYDROCARBON RADICALS CONTAINING 1 TO 12 CARBON ATOMS SELECTED FROM THE GROUP CONSISTING OF ALKYL, ARYL AND ARALKYL, THE MOLAR RATIO OF COMPONENT 1 TO COMPONENT 2 TO COMPONENT 3 IN SAID CATALYTIC MIXTURE BEING WITHIN THE RANGE OF 1:4:0.1 TO 16:1:1.
 9. AS A COMPOSITION OF MATTER, A POLYMERIZATION CATALYST CONTAINING (1) A NONDISTILLABLE POLYMERIC SOLID REACTION PRODUCT OF A METHYLENE HALIDE WITH A METAL FROM THE GROUP CONSISTING OF ALUMINUM, ZINC AND MAGNESIUM (2) A TITANIUM COMPOUND SELECTED FROM THE GROUP CONSISTING OF TITANIUM HALIDES, TITANIUM ALKOXIDES AND TITANIUM OXIDES, AND (3) A COMPOUND OF A GROUP VA ELEMENT SELECTED FROM THE GROUP CONSISTING OF NITROGEN, PHOSPHORUS, ARSENIC AND ANTIMONY AND EACH R IS A RADICAL SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND HYDROCARBON RADICALS CONTAINING 1 TO 12 CARBON ATOMS SELECTED FROM THE GROUP CONSISTING OF ALKYL, ARYL AND ARALKYL, THE MOLAR RATIO OF COMPONENT 1 TO COMPONENT 2 TO COMPONENT 3 IN SAID CATALYTIC MIXTURE BEING WITHIN THE RANGE OF 1:4:0.1 TO 16:1:1. 